CN103407296A - Method for achieving high-melting-point material 3D printing through nanometer ink together with laser melting - Google Patents
Method for achieving high-melting-point material 3D printing through nanometer ink together with laser melting Download PDFInfo
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Abstract
The invention discloses a method for preparing the nanometer ink through ceramics, metal, semiconductors, glass and other high-melting-point materials, carrying out 3D printing and utilizing the laser heating sintering in the process of printing to obtain 3D devices formed by combining the ceramics, the metal, the semiconductors and other composite. The method comprises the first step of processing raw materials needed to prepare the device into nanometer particles of 1-500nm, the second step of preparing the particles into ink jet printing ink, the third step of carrying out 3D printing by utilizing an improved ordinary ink printer and adopting the laser heating sintering in the process of printing, and the fourth step of achieving the melting and sintering molding of the nanometer particles. According to the method, micron-level precision devices with any complex shape can be directly prepared, the high surface energy of the nanometer particles is utilized, the sintering temperature is lowered, high density is achieved, and a superior property is obtained. The method can be used for manufacturing automobile metal ceramic composite pistons, aviation engine tail pipes, and ceramic bearings and ceramal composite precise components of watches and other precision instruments and for directly printing a circuit board.
Description
Technical field
The present invention relates to inkjet printing and advanced manufacturing technology field, relate in particular to the laser sintered and 3D of nano particle and print, particularly about the laser sintered ink that contains nano particle, prepare the Method of printing of high accuracy, high-performance, high-melting-point composite 3D device.
Background technology
3D print be a kind of be to take Computerized three-dimensional to design a model as source, discrete and the numerical control molding system by software hierarchy, utilizing the modes such as laser, hot melt nozzle that the special materials such as metal dust, ceramic powders, plastics are successively piled up coheres, final stack moulding, produce the technology of entity products.Traditional manufacture is produced device by mould, machining mode, and the process-cycle is long, and equipment needed thereby is many.And the 3D printing technique is complicated 3D solid to be become to the combination of several simple two dimensional surfaces, by material successively overlap-add procedure obtain finished product.The 3D printing technique the exploitation of complex parts processing, new product and single and mini-batch production part produce and isolation environment under the part processing and other fields of (as spaceport, ocean-going ship etc.) have great advantage.
The major technique of 3D printing at present comprises Stereolithography (Stereo Lithigraphy Apparatus, SLA), fusion sediment moulding (Fused Deposition Modeling, FDM), laminated solid body processing (Laminated Object Manufacturing, LOM), three dimensional printing (Three Dimension Printing, 3DP), selective laser sintering (Selective Laser Sintering, SLS) etc.
Stereolithography (SLA) is in 1984, to obtain United States Patent (USP) (United States Patent (USP) 4575330) by Hull and Charles W., is the rapid shaping technique grown up the earliest.The forming process of Stereolithography technique is to take photosensitive resin to be raw material, makes its Layer by layer solidification moulding by the computer control Ultra-Violet Laser.This method can simple and direct, automatically produce the prototype that surface quality and dimensional accuracy are higher, geometry is more complicated.The shortcoming of Stereolithography is: in (1) forming process, be accompanied by physical and chemical changes, product is more flexible, needs to support, otherwise can cause the product distortion; (2) performance of liquid resin after solidifying is not as industrial plastic commonly used, generally more crisp, easy fracture; (3) equipment operation and maintenance cost are higher.Because the price of liquid resin material and laser instrument is higher, and, in order to make optical element be in desirable duty, need to carry out regular adjustment and strict space environment, its expense is also higher; (4) material category of using is less.Available material is mainly photosensitive liquid resin material at present, and liquid resin has certain smell and toxicity, and needs the lucifuge protection; (5) under many circumstances, the prototype resin after the rapid prototyping system photocuring, not fully by laser curing, for improving serviceability and the dimensional stability of model, needs regelate usually.
Fused Deposition Modeling (FDM) technique was succeeded in developing (United States Patent (USP) 5121329) by American scholar Crump and Scott in 1988.The material of FDM is generally thermoplastic, as wax, ABS, nylon etc., with thread feed.Material is heated fusing in shower nozzle, shower nozzle is along the part section profile and fill orbiting motion, simultaneously the material of fusing is extruded, and material solidifies rapidly, and with on every side condensation of materials.Shortcoming is: the material that (1) is selected is confined to wax, ABS, the nylon of low melting point; (2) there is obvious striped on the surface of profiled member; (3) along the strength ratio of shaping axle vertical direction a little less than; (4) need the design and fabrication supporting construction; (5) need to scan coating to whole cross section, molding time is longer.
Laminated solid body processing (LOM) is that Feygin and the Michael by U.S. Helisys company succeeded in developing (United States Patent (USP) 4752352) in 1986.LOM process using sheeting, as paper, plastic sheeting etc.Sheet surface applies the last layer PUR in advance.Add man-hour, hot-pressing roller hot pressing sheet material, make it bonding with following in type workpiece.Use CO
2Laser instrument cuts out part section profile and workpiece housing on just bonding new layer, and between cross section profile and housing, cuts out the grid of consistency from top to bottom in unnecessary zone.After laser cutting completed, workbench drove in type workpiece and descends, with banded sheet separation.Feeding machanism rotates collecting shaft and feed axle, drives material strip and moves, and makes new layer move on to machining area.Work is closed and is raised to processing plane, hot-pressing roller hot pressing, and the number of plies of workpiece increases one deck, highly increases a material thick.Cutting section profile on new layer again.So repeatedly until all cross sections of part bonding, cut.Finally, remove the redundance of chopping, obtain the entity component that layering is manufactured.LOM technique only need cut out the profile of part section on sheet material, and need not scan whole cross section.Therefore the speed of moulding thick-walled parts, be easy to manufacture heavy parts.In technical process, there do not is material phase transformation, therefore be difficult for causing buckling deformation.Excess stock work in-process between workpiece housing and cross section profile has played supporting role, so LOM technique is without adding support.Shortcoming is that Material Used is confined to the sheet materials such as fibrous paper, plastic foil, and forward and backward processing is wasted time and energy, and can not manufacture hollow structural members.
Three-dimensional printing art (3DP) is (United States Patent (USP) 5340656) of the people such as the E-manual Sachs of Massachusetts Institute Technology development.3DP process using forming material powder, as ceramic powders, metal dust.Difference is that material powder is not by sintered bond, but by shower nozzle binding agent (as silica gel) by the cross section of part " printing " on material powder.Shortcoming is lower by the bonding part strength of binding agent, and compactness is poor, also must post processing.
Selective laser sintering (SLS) is that the C.R.Dechard by the Austin of Texas ,Usa university branch school succeeded in developing (United States Patent (USP) 4863538) in 1989.SLS technique is utilized the dusty material moulding.Material powder paving is sprinkled upon to the upper surface of molded part, and strikes off, use high-intensity CO
2Laser instrument scans part section on the new layer just spread, material powder is sintered together under high-intensity Ear Mucosa Treated by He Ne Laser Irradiation, obtain the cross section of part, and is connected with following in type part.After a layer cross section sintering is complete, spread new layer of material powder, selectively layer cross section under sintering.After sintering completes, remove unnecessary powder, then polish, the processing such as oven dry obtains part.The characteristics of SLS technique are that the material adaptation is wide, can not only manufacture plastic part, can also manufacture the part of the materials such as pottery, wax, particularly can manufacture metal parts.This makes SLS technique have much attraction.SLS technique is without adding support, because do not have the powder of sintering to play the effect of supporting.But (SLS) technology can only be selected lower metal and the ceramic powders of fusing point of special component.Especially when preparing metal device, due to thermograde and thermal stress larger, resulting devices often exists more pore, shrinkage cavity, defects i.e.cracks.
Current 3D printing technique has significant limitation on material is selected, therefore most product is all the sample for body observation, but not true available device.Even if Material Used is selective laser sintering (SLS) technology comparatively widely, also can only select lower metal and the ceramic powders of fusing point of special component.Therefore at present the product printed of 3D the performances such as precision, mechanical property and heat, electricity, light, magnetic usually and expection greatly differ from each other.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides a kind of method that lf aided nano ink realizes that materials with high melting point device 3D prints.This method is prepared as nano particle by material, then is prepared as nanometer particle ink, and the general commercial ink-jet printer by repacking carries out the 3D printing, in print procedure, adopts LASER HEATING, realizes melting, sintering and the moulding of nano particle.The method is applicable to the high-molecular organic materials such as dystectic material such as metal, pottery, glass, semiconductor and plastics simultaneously, metal material comprises one or more in gold, silver, copper, zinc, aluminium etc., pottery comprises one or more in alundum (Al2O3), zirconia etc., semiconductor comprises one or more in silicon, germanium etc., organic polymer comprises polyacrylic resin, PMA, one or more in polyethylene etc.The invention solves in existing 3D printing technique the material range of choice narrow, printing head is few, the technical problem that print speed is slow.
The method applied in the present invention is that material is prepared as to nanometer particle ink, in conjunction with laser sintered, carries out high accuracy 3D printing, and prepares the 3D device, and the step of the method comprises:
(1) will be prepared into the diameter nano particle for the material that the 3D device is printed, the diameter of nano particle is the 1-500 nanometer, preferably 1-200 nanometer, more preferably 20-100 nanometer, most preferably 30-50 nanometer; The material of printing for the 3D device comprises the high-melting-point inorganic material such as metal, pottery, glass, semiconductor and comprises the macromolecular material of the low melting points such as plastics, rubber, fiber.
(2) nano particle prepared by step (1) is prepared as and is applicable to the nanometer particle ink that the 3D ink-jet printer is used, and ink composition comprises nano-particle material and regulates ink performance makes it adapt to the various chemical substances of inkjet printing;
(3) according to shape and the performance requirement of resulting devices, carry out three-dimensional modeling and 3-D graphic is divided into to some layers of X-Y scheme, the shape and the material that calculate every one deck two dimensional surface form, design printing path, according to composition and the diameter of nano particle, calculate melting, sintering temperature and time simultaneously;
(4) nanometer particle ink step (2) made is packed into the 3D ink-jet printer of laser sintered function, print subsequently, sintering, successively stack, realize the printing of 3D device, wherein, described printing, sintering process is carried out as follows: the printing path that the 3D ink-jet printer is determined according to step (3) carries out the printing of every one deck X-Y scheme, the zone of just having printed with laser preheating zone to be printed and high-temperature heating during printing, the volatilization of the material except nano particle in ink and the melting of nano particle are realized in the zone that heating has just been printed, sintering and moulding, after this carry out the printing of lower one deck X-Y scheme, so successively stack forms the 3D device.
In method provided by the invention, three-dimensional modeling also is divided into some layers of X-Y scheme by 3-D graphic, calculates the shape of every one deck two dimensional surface and material and forms, and designs the operation principle such as printing path the same with traditional 3D printing with step.Wherein, can save the three-dimensional modeling process, the model that directly uses existing digital three-dimensional software to provide.
In method provided by the invention, successively print procedure is identical or similar with traditional 3D Method of printing, namely the 3D device that will print is decomposed into to multilayer, then successively prints and superposes.
In method provided by the invention, the temperature of the diameter control heating region by regulating laser power and LASER SPECKLE is at suitable temperature and keep reasonable time.The temperature and time kept is determined according to the character of nano material and the performance of required device.
In method provided by the invention, in heating process, pass through the temperature of infrared temperature sensor Real-Time Monitoring heating region.
In method provided by the invention, print, sintering process carries out in the inert atmospheres such as vacuum or argon gas, nitrogen, helium.
The present invention also provides a kind of 3D ink-jet printer of realizing materials with high melting point device 3D Method of printing for lf aided nano ink, and it is converted by general commercial 3D ink-jet printer.
3D ink-jet printer of the present invention specifically comprises:
Providing ink part and pattern printing portion with general commercial ink-jet printer;
Have a platform of can lifting and moving forward and backward and be used for carrying print media, this platform one deck that descends after every printing, sintering one patterned layer, make the distance of printing between plane and inkjet printer head keep a fixed value, is generally 2-10mm; This platform can move forward and backward to realize the high accuracy printing of large area pattern in print procedure;
Has the adjustable generating laser of power and spot diameter, the zone that this generating laser emission multiple laser has just been printed in order to preheating zone to be printed heating;
Have infrared temperature sensor, this infrared temperature sensor is for the Real-Time Monitoring of temperature;
Possess computer board, this computer board connects generating laser and infrared temperature sensor, accepts the temperature signal of infrared temperature sensor, according to the temperature signal regulating-controlling program and it is fed back to generating laser;
Possess vacuum or atmosphere adjustment device, it can be, and 3D prints, sintering process is passed through vacuum or inert atmosphere.
Compared with prior art, advantage of the present invention is:
(1) the material range of choice is wide, and most metal, pottery, glass and macromolecular materials can be suitable for;
(2) nano particle has large specific area, and surface can be high, and fusing point significantly reduces, and has reduced melting, sintering temperature, has not only saved the energy and has also made the 3D printing of materials with high melting point become relatively easy.And the nano particle diameter is little has again high interface energy, and the low-temperature sintering process can realize densified, avoids shrinkage cavity, defects i.e.cracks.
(3) the ink-jet printer nozzle hole number is large, can effectively improve the speed that traditional 3D prints.
The specific embodiment
In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention is described in more detail below in conjunction with specific embodiment.
Embodiment 1:
Step 1, at first zinc, aluminium, copper and magnesium are prepared as to the nano particle of diameter 50-100nm, and are made into nanometer particle ink;
Step 2, according to the three-dimensional modeling requirement of device, carry out three-dimensional modeling and 3-D graphic is divided into to some layers of X-Y scheme, the shape and the material that calculate every one deck two dimensional surface form, design printing path, composition and the diameter of the nano particle used as required simultaneously, calculate melting, sintering temperature and time;
In step 3, forming cavity, vacuumize and pass into argon gas as protective atmosphere, according to the proportioning of 74.5% zinc, 22% aluminium, 3% bronze medal, 0.5% magnesium, carry out the 3D inkjet printing;
(4) in the 3D ink jet printing process, use the laser scanning print area, controlling spot diameter is 1-100 μ m, sweep speed is 0.001-1000mm/s, heating-up temperature is 50-800 ℃, make the various material volatilizations except nano particle in the ink in firm printing, make simultaneously the nano particle melting and be connected to the body material;
(5) successively print sintering, successively stack, obtain resulting devices.The hardness of device is 70-80HV, and percentage elongation is 3200%, and performance is better than the conventional cast device (hardness 50-60HV, percentage elongation are 2500%) of same sample ingredient.
Embodiment 2:
(1) at first titanium dioxide, aluminium oxide, zinc, aluminium, copper, magnesium are prepared as to the nano particle of diameter 50-100nm, and are made into ink;
(2) according to the three-dimensional modeling requirement of device, carry out three-dimensional modeling and 3-D graphic is divided into to some layers of X-Y scheme, the shape and the material that calculate every one deck two dimensional surface form, design printing path, composition and the diameter of the nano particle used as required simultaneously, calculate melting, sintering temperature and time;
(3) in forming cavity, vacuumize and pass into argon gas as protective atmosphere, according to figure output requirement, carrying out the 3D inkjet printing;
(4) in the 3D ink jet printing process, in conjunction with infrared remote sensing and laser sintered technology, controlling spot diameter is 1-100 μ m, and sweep speed is 0.001-1000mm/s, and heating-up temperature is 50-2800 ℃;
(5) obtain resulting devices after successively printing sintering.Device surface is white, and at 150N, under 200r/min, coefficient of friction is 0.12, hardness is 230-250HV, in the NaCl of the room temperature 3.5wt-% aqueous solution, soak 72h, the corrosion-free phenomenon in top layer, solved the poor problem of soft, corrosion resistance of the superplasticity allumen of traditional metallurgical gained.
Embodiment 3:
(1) at first by a kind of nano particle that is prepared as respectively diameter 50-100nm in polyacrylic resin and argent, copper, aluminium, and be made into nano-resin particle ink and nano-metal particle ink;
(2) according to the design of circuit board, carry out three-dimensional modeling and 3-D graphic is divided into to some layers of X-Y scheme, calculate pattern and ink used (the conductive region metallic ink of every one deck two dimensional surface, insulating regions resin ink), design printing path, calculate simultaneously melting, sintering temperature and time;
(3) in forming cavity, vacuumize and pass into argon gas as protective atmosphere, according to figure output requirement, carrying out the 3D inkjet printing;
(4) in the 3D ink jet printing process, adopt the ink-jet simultaneously of two groups of shower nozzles, one group of shower nozzle is used the pattern of resin ink printed insulating regions, another group shower nozzle to use metallic ink to print the pattern of conductive region, in conjunction with infrared remote sensing and laser sintered technology, controlling spot diameter is 1-100 μ m, sweep speed is 0.001-1000mm/s, and heating-up temperature is 80-200 ℃;
(5) successively print after sintering and obtain final multilayer circuit board.
Claims (13)
1. the Method of printing of a 3D device, comprise the steps:
(1) will be prepared into nano particle for the material that the 3D device is printed;
(2) nano particle of step (1) is prepared as and is applicable to the nanometer particle ink that the 3D ink-jet printer is used;
(3) according to shape and the performance requirement of 3D device, carry out three-dimensional modeling and 3-D graphic is divided into to some layers of X-Y scheme, calculating shape and the material of 3D device on every one deck X-Y scheme forms, design printing path, according to composition and the diameter of nano particle, calculate melting, sintering temperature and time simultaneously;
(4) ink prepared by step (2) is packed into the 3D ink-jet printer of laser sintered function, print subsequently, sintering, successively stack, realize the printing of 3D device, wherein, described printing, sintering process is carried out as follows: the 3D ink-jet printer carries out the printing of every one deck X-Y scheme according to the printing path that step (3) obtains, the zone of just having printed with laser preheating zone to be printed heating during printing, the zone that heating has just been printed makes the volatilization of the material except nano particle in ink, and make the nano particle melting, sinter molding, print, after sintering, carry out the printing of next layer X-Y scheme, the final 3D device that forms.
2. according to the method for claim 1, the material of printing for the 3D device in step (1) comprises high-melting-point inorganic material and low melting point organic material.
3. according to the method for claim 2, described inorganic material comprises pottery, metal, glass, semiconductor, and described organic material comprises plastics, rubber.
4. according to the method for claim 1, in step (1), the diameter of nano particle is the 1-500 nanometer.
5. according to the method for claim 4, the diameter of nano particle is the 1-200 nanometer.
6. according to the method for claim 5, the diameter 20-100 nanometer of nano particle.
7. according to the method for claim 1, the nanoparticle inks water constituent in step (2) comprises nano particle and be used to regulating the various chemical substances of ink performance.
8. according to the method for claim 1, printing, sintering process in step (4) are carried out under vacuum or inert atmosphere.
9. according to the method for claim 9, described inert atmosphere comprises argon gas, nitrogen and helium.
10. according to the method for claim 1, in the heating process of step (4), the temperature of the diameter control heating region by regulating laser power and LASER SPECKLE is at suitable temperature and keep reasonable time, uses simultaneously the temperature of infrared temperature sensor Real-Time Monitoring heating region.
11. according to the process of claim 1 wherein that the 3D ink-jet printer reequiped by the general commercial ink-jet printer.
12. the ink-jet printer of the 3D for the described method of claim 1 to 11, it is converted by the general commercial ink-jet printer, is characterised in that:
Providing ink part and pattern printing portion with general commercial ink-jet printer;
Have a platform of can lifting and moving forward and backward and be used for carrying print media, this platform one deck that descends after every printing, sintering one patterned layer, make the distance of printing between plane and inkjet printer head keep a fixed value; This platform can move forward and backward to realize the high accuracy printing of large area pattern in print procedure;
Has the adjustable generating laser of power and spot diameter, the zone that this generating laser emission multiple laser has just been printed in order to preheating zone to be printed heating;
Have infrared temperature sensor, this infrared temperature sensor is for the Real-Time Monitoring of temperature;
Possess computer board, this computer board connects generating laser and infrared temperature sensor, accepts the temperature signal of infrared temperature sensor, according to the temperature signal regulating-controlling program and it is fed back to generating laser;
Possess vacuum or atmosphere adjustment device, it can be, and 3D prints, sintering process is passed through vacuum or inert atmosphere.
13. according to the 3D ink-jet printer of claim 12, the distance of wherein printing between plane and inkjet printer head is 2-10mm.
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